Acid and quaternary salts of polyamides



Patented Jan. 29, 1952 ACID AND QUATERNARY SALTS OF POLYAMIDES Lewis 0.Gunderson, Park Ridge, 11]., assignor to Dearborn Chemical Company,Chicago, 111., a corporation of Illinois No Drawing. ApplicationFebruary 12, 1949,

Serial No. 76,191

14 Claims.

This invention relates to new and novel compositions of matter, andparticularly to acid and quaternary salts of polyamides.

The present application is a continuationinpart of application No.25,983, filed May '8, 1948, entitled Method and Composition for WaterConditioning.

An object of the present invention is to provide high molecular weightwater-dispersable compounds, useful as foam inhibiting compounds,flotation agents in mineral and material separation, and demulsificationcompounds.

A further object of the present invention is to provide novelderivatives of polyamides which are useful as wetting agents, resinintermediates, pharmaceutical intermediates, and the like.

The compounds of the present invention have the following generalformula:

where R4, R5, R6, R1 and Rs are alkylene groups, R1 and R9 arehydrocarbon groups containing at least 11 carbon atoms, R2 is selectedfrom the group consisting of alkyl, alkoxy, substituted alkyl, andsubstituted alkoxy groups, R3 is an alkyl group, X is an anion of amineral acid, Y is selected from the group consisting of hydrogen andacyl radicals, Z and Z are selected from the group consisting ofhydrogen and alkyl radicals,

m,nandpare0,1or2,andyisor1.

These compounds comprise the reaction product formed between asolubilizing agent such as dimethyl sulfate, dimethyl sulfite, methylchlo ride, methyl iodide, B, B dichloro diethyl ether, benzyl chloride,ethyl p-toluene sulfonate, and the like, and a polyalkylene polyaminethat has been subjected to acylation with a higher carboxylic acid to anextent such that at least two acyl groups have been attached to thepolyalkylene polyamine.

The term solubilizing agent'includes those compounds having the abilityto replace one 01' more of the hydrogens of an amino group with alkylgroups. H

The organic compounds to which the present invention particularlyrelates comprise high molecular weight acylation products ofpolyalkylene polyamines, such" as diethylene triamine, triethylenetetramine, tetraethylene pentamine, and other polyethylene polyamines,dipropylene triamine, tripropylene tetramine, di-isopropylene triamine,tri-isopropylene tetramine, dibutylene triamine, and the like. Otherpolyalkylene polyamine compounds may also be used; for instance,polyalkylene polyamine compounds characterized by heterogeneous linkageswithin the molecule, such as an ether, thio, thionyl, or aromaticradical as Well as the polyamides resulting from the reaction of apolyethylene polyamine, e. g., diethylene triamine, with a dibasic acid,e. g., succinic acid, in molar proportions of two to one. Thesepolyalkylene polyamine compounds are condensed with non-aromaticcarboxylic acids containing at least 12 and preferably at least 16carbon atoms. Such non-aromatic carboxylic acids may be substituted orunsubstituted, straight or branched chain, or cyclic, and saturated orunsaturated. Thus, carboxylic acids other than those present in orderived from vegetable and animal fats and oils may be used, forinstance, naphthenic acids. The resultin polyalkylene polyamidecompounds may comprise in part high molecular weight fatty acids and inpart other high molecular weight carboxylic acids and/or cyclic acids.ing acids are oleic acid, stearic acid, palmitic acid, erucic acid,linoleic acid, linolenic acid, ricinoleic acid, palmitated ricinoleicacid, monohydroxy stearic acid, dihydroxy stearic acid, cetyloxy butyricacid, behenic acid, keto-hydroxy stearic acid, lauric acid, highmolecular weight naphthenic acids, and the various aldehyde acids whichmay be prepared from ricinoleic acid.

In connection with the use of fatty acids as acylating agents, it shouldbe noted that commercial fatty acids always contain more than. onespecies of acid. When using such commercial" reagents, it is quitelikely that the acylating groups will vary in chain length and hydrogencontent. Thus, R; and R9 depicted in. the gen eral formula could easilybe different groups;

The high molecular weight polyamides may be prepared by condensing apolyalkylene polyamine with a non-aromatic carboxylic acid or aderivative thereof, such as an ester, anhydride, or halide in suchproportions and under such conditions as to efiect at leastmonoacylation of both non-aromatic carboxylic acid, a fatty acid, afatty it Examples of such acylat- 3 glyceride, or an acyl halide, inappropriate molecular proportions as, for example, with one or moremoles of fatty acid for each mole of polyalkylenepolyamide. I have foundthat reacting a fatty acid, e. g., stearic acid, with a polyamine, e.g., diethylene triamine, in equi-molecular ratio at a temperature ofabout 175. C. ($20" C.) will result in the production of the diamide asthe predominant reaction product, with only a small amount of themonoamide being produced. The

heating may be carried out for from two to six.

hours or more at a temperature of about 140 C. and up. For thepreparation of 'triacylated or. tetracylated compounds from polyalkylenepolyamines containing two or more secondary amino roups, a temperatureof 175 C. or higher is preferred. r From the polyalkylene polyamides ofhigher fatty acids'prepared as described hereinabove, the acid andquaternary salts of the polyamides may be prepared by reacting thepolyalkylene polyamides, with an amine-alkylating agent such asdimethylsulfate or dimethyl sulfite. In gen- 'eral, at least ne molecularproportion of dimethyl sulfate or'dimethyl sulfite is used in con- Vjunction with one molecular proportion of poly- 'alkylene polyamide.When a one-to-one molecular ratio is employed, the resulting productsare salts of the monomethylated derivatives of the polyalkylenepolyamides, When dimethyl sulfate is employed, the salts of the methylsulfuric acid are obtained. When dimethyl sulfite is employed, the saltsof the corresponding sulfinic acids are obtained.

'By way of example: By starting with triethylene tetramine that has beendiacylated in the primary amino groups with a compound such as stearic.acid, thus leaving two secondary amino groups in the molecule, upon theaddition of the first mole of dimethyl sulfate, the methyl sulfuric acidsalt will form on one of the secondary amino groups.

. upon the addition of two moles of dimethyl sulfate.

of dinaphthenoyl diethylene triamine, R being a naphthenic acid residue.

Dimethyl ammonium'methyl sulfate quaternary salt of the diricinoleamideof diethylene triamine.

Dimethyl ammonium methyl sulfate'quaternary salt of dipalmitoyldiethylene triamine.

' B. Compounds having two quaternary ammonium groups as well as asecondary amide group in the molecule:

Di-methyl ammonium methylsulfate quaternary salt of trinaphthenoyltetraethylene pentamine,

R1 representing a naphthenic acid residue.v

C. Compounds having on quaternary ammonium group as well as a. pluralityof secondary amide groups:

' Dimethyl ammonium iodide quaternary methyl- In generalfthe dimethylsulfate or dimethyl sulflte may simplyfbe'added to the 'polyalkylenepolyamine and such heat suppliedas may be required'for completing thereaction. If desired, a solvent, such as pyridine, maybe used, or an.alkali may be added tolthe reaction mixture.

The polyalkylene polyamide mayfalso be acylated'within the molecule bymeans of short chain ride or acetic anhydride.

vThe following examples are illustrative of the types of compoundsfalling within the scope of Dimethyl ammonium methyl sulfinatequaternary acylating compounds, for example, acetyl chloamine iodidesalt of, dinaphthenoyltriethylene tetramine. R1 represents a naphthenicacid residue.

E. Compounds having, a quaternary ammonium group, a tertiary amine salt,and a secondary amide group:

oH osor I CH3 OSOr V HN-C nil-N- 0 1H ,1 rc 2H4-N-O zH'4-NH in R1 I 1'Dimethyl ammonium methyl sulfatequaternary methylamine methylsulfuricacid salt of trinaphthenoyl 'tetraethylene pentamine, wherevRrrepresents a residue from a naphthenic acid.

-1 Methyl sulfuric acid salt of N-methyl, N, N" stearoyloleoyldiethylene triamine.

CHsPSOz' HN-CzH4-NC2H4NH Methyl sulfinic acid salt of N-methyl, N, 'Ndinaphthenoyl diethylene triamine. R. represents Methyl sulfuric acidsalt of N-methyl, N, N", distearoyl triethylene tetramine. Y

Condensation product obtained by reacting triethylene tetramine withsoybean oil in equirnolecular amounts and then treating the resultingpolyamide with one mole of dichloroethyl ether. R1 represents any of thefatty acid groups containing at least 11 carbon atoms present in thesoybean oil.

G. Compounds having more than one tertiary amine salt group:

.Di-(methyl sulfuric acid salt) of N-methyl, N methyl, N"; N'dilinolenoyl triethylene tetramine.

H. Compounds having a tertiary amine salt group and a secondary amideradical:

Methyl sulfuric acid salt of N -methyl, N, N tripalmitoyl tripropylenetetramine.

I. Compounds having two tertiary amine salt groups and a secondary amidegroup: CHaPSOa CHEPSOQ' nN-oH.-No2mN=o2H.-N=orr.-NH

nHan 511 35 nHss Di(methyl sulfuric acid salt of N-methyl), N. N", Nstearoyl dioleoyl tetraethylene pentamine. The preparation of thecompounds of the pres.- ent invention is illustrated by the examplesgiven hereinb elow Example I 8.8 gr. soybean oil, 2 gr. tetraethylenepentamine and 0.6 gr. water were heated in a flask, first for one-halfhour on a steam'bath, and thereafter for 2 hours at 150 C. Aftercooling, 1.3 gr. dimethyl sulfate were added. The temperature thereuponinitially rose tof90' C. When the reacting mixture began to cool, heatwas applied, the final temperature one hour after.the

addition of the dimethyl sulfate being 148 C. 11.9 gr. of a clearviscous oil were obtained. A tertiary amine salt of the type shown ingroup F was produced. 1

Example II 8.8 gr. soybean oil, 1.5 gr. triethylene tetramine (1:1 moleratio), and 0.6 gr. water were heated, first forone-half hour in a steambath and thereafter for. 2 hours at 156 C., yielding 10.1 gr. of a waxhaving a saponification number 7 of 3.9, 8.9 gr. of this wax were mixedwith gr.

, dimethyl sulfate. When the reaction mixture began to cool, heat wasapplied to raise the temperature to 153 C. .After one-half hour therewas obtained a clear viscous oil dispersible in water. The product was amixture of the types of compounds shown in groups F and H.

Emample III i 58.5 gr. soybean oil, 10.8 gr, triethylene tetramine (96%)and 5.3 gr. acetic anhydride were heated together for 8 hours at from132 to 159 C., yielding a dark brown clear viscous oil characterized byan acid number of 15.8. On standing, the oil formed'a paste having amelting point of C. 7.4..gr. of the paste and 1.3 gr. dimethyl sulfatewere stirred together in a test tube to form a clear homogeneous oil.The temperature rose from 22 to 45 C. One gram of the resulting oil was.found to'be dispersible in 10 cc. of water. A waxy precipitate wasobtained on addition of 10% sodium carbonate solution, indicating thatthe amine salt had been formed, of the type represented by group F.

Example I V Oleio acid and triethylene tetramine in molecularproportions of 2:1 were heated together for 6 hours at from to 161 C.and thereafter for three hours at from 143 to 158 C., yielding a productcharacterized by an acid number of 3.28. 13.2 gr..of the resulting amidewere heated to just above itsmelting point and 5 cc. (6.75 gr.)0fdimethyl sulfate was then added dropwise. The temperature rose to 140C.., and this temperature was maintained for /g hour to complete thereaction. The final product could be dispersed in water as a 2%dispersion. The product was probably a double amine salt of thetyperepresented by group G. 1

Example V Triethylene tetramine and oleic acid were reacted together asdescribed in Example IV. 13.2 gr. of the resulting product was heated tojust above the melting point, and 10.1 cc. (13.6 gr.) of dimethylsulfate was introduced dropwise. The temperature rose to 140 C., andthistemperature was maintained for hour to complete the reaction. Thefinal product could be dispersed in water as a 2% solution. The reactionproduct was probably a mixture of the types 0 compounds disclosed ingroups B and D.

Example VI 29.2 gr. triethylene tetramine and 113.6 gr. of stearic acidwere heated at about C. for 6 hours. The reaction made was then allowedto cool to 125 C. and 43 gr. of dimethyl sulfite were added gradually.The initial reaction was exothermic, the temperature risingspontaneously to 135 C. (during the addition of 30 gr. of dimethylsulfite). When no more heat was generated, the mixture was refluxed at110 C; for 6 hours. After cooling, the reaction mixture 'waslpouredgroup F.

into benzene, the resulting hot solution filtered,

1 and the filtrate was cooled to. C. to crystallize compoundsrepresentedby group D.

1 a Example VII Triethylene tetramine was heated with lauric acid'-(prepared from coconut fatty acids-by removal of fatty acids containingless than 12 carbon atoms) in molecular proportion of 3:1. Thetemperature was kept at 150 to 160C. for more than 12 hours. 7 20.1 gr.of the resulting product was heated with 2.7 gr. of dimethyl sulfate forhour at 153 to 155 C. The final product was a dark brown waxy soliddispersible in water. The product was of the type represented bythoseingroup H.

' I Example VIII Triethylene tetramine (14.6 gr. or 0.1 mole) was heatedwith 6.0 gr. mole) of water and 96;6 gr.-(0.3 mole) of naphthenic acid(a mixture of carboxylicacids recovered from crude petroleum having anaverage acid number of 174)- for A.; hour at 85 to 90 C. and then for 2hours at 155 C.

-To 68.4 grnof the resulting polyamine' was added 8.3 gr. of dimethylsulfate (equimolar ratio). This addition caused: a rise in temperaturefrom 33 to 68 C. External heat was then applied until a temperature of153 C. was reached. This temperature was .maintained for hour."

The crudefinal product is essentially a methyl sulfuric acid salt of amethylated polynaphthenic amide of triethylene tetramine of the typeshown in group H. It is a highly viscous black colored oil.

Example IX "Triethylene tetramine (14.6 gr. or 0.1 mole) was heatedwith96.6 er. (0.3 mole)v of naphthenic acid for 6 hours at 180 C. Theproduct. is. a highly viscous black oil.

This naphthenic polyamide was then treated with 29.4 gr. (0.2 mole) ofmethyl iodide. Heat was liberated spontaneouslyat the start. Thenexternal heat was applied and a temperature. of

150 C. held;for 2hours.

The final product isa quaternary-derivative of the original naphthenicamide. This.v type of compound is represented by group C; It is a blackcolored waxy solid.

Example X 8.8 gr. of soybean oil was added to a solution of 1.5gr.-triethylene tetramine and 0.6 gr. water.

This mixture was heated for hour at 90 C.

and for two hours at 140 C.

To the resulting polyamide was then added 1.9 gr. of triglycoldichloride and the mixture heated for four hours at 140 C. The resultingproduct is a brown paste-likemass. The product is a tertiary aminesaltof the type shown in Example XI 03 gr. of soybean oil: was added to asolution 012.0 gr. of tetraethylene pentamine and 0.6. gr.

Example XI'I 8.8 gr. of soybean oil wasadded to 1.5 gr. of triethylene.tetramine and the mixture heated at C. for 6 hours. The resulting lightbrown colored wax was then treated with 1.3 gr. of dimethyl sulfate for2 hours at 150 C. The methylated polyamide obtained in this manner wasthen converted to the corresponding quaterv nary ammonium salt byheating for 2 hours at 150 C. with 1.9 gr. of the methyl ester ofp-toluene sulfonic acid. 7

Example XIII One molecular proportion of tetraethylene pentamine wascondensed with three molecular proportionsof a naphthenicacid having aneutraliz ation equivalent of 300 at 190 C. i 10 0. for-a period of 8hours. The water insoluble polyamide was-reacted with dimethyl sulfateinmole ratioi of about 1:5 until the alkylation was substantiallycomplete. The water dispersiblerprodnot: was: a di-methyl ammoniummethyl sulfate quaternary salt of trinaphthenoyl tetraethylenepentamine, the: type of compound shown. in

group B. r

. Example XIV The reactions of ExampleXIII were repeated in all respectsexcept that the mole ratio in the final condensation was changed to 1:3.The

reactionproduct was the dimethylammonium methylsulfate quaternary-methylamine methyl sulfuric acidsalt of-tri-naphthenoyl tetraethylenepentamine, a type of compound shown in group E.

Example XV The reactions of Example XIII were again repeated in allrespects except that the mole ratio in the final condensation waschanged to 1:2. The resulting product was the di(methyl sulfuric acidsalt, of N-me-thyl) N, N, N" trinaph- 'thenoyl tetraethylene pentamine,a type of com pound shown in'group G. r

ExampleXVI One molecular proportion of diethylene' tri-l amine wascondensed with two molecular proportions of palmitic. acid at atemperature of C. for six hours. The resulting diamide was reacted withtwo molecular proportions of dimethyl sulfate, the latter beingintroduced slowly into thediamide reaction productuntil all. thealkylati ng agent had been added. Thereafter, the temperature was raisedto 140 C. and maintained attha't temperature for hour. j The reaction.product was dispersible in water and was not precipitated when thesolution was made alkaline, indicating the formation of a quaternaryammonium salt. This type of compound is shown ingrouplA. i1- claim asmy'invention:

l. A compound having the formula;

' (Rs) ,,X- R3 ,x'

where R1, R5, R6, R1 and Rs are short chain alkylene groups containing 2to 3 carbon atoms, R1 and R9 are aliphatic hydrocarbon groups containingat least 11 carbon atoms, R2 is a hydrophilic group containing an alkylchain of one to two carbon atoms, R3 is short chain alkyl group, X is anion selected from the group consisting of sulfate, sulfonate and halideions, Y is selected from the group consisting of hydrogen and carboxylicacyl radicals, Z and Z' are selected from the group consisting ofhydrogen and short chain alkyl radicals, but where Z and Z are alkyl, Yis acyl, m, n and p are 0, 1 or 2, and y is or 1.

'2. A compound having the formula:

R3 is a short chain alkyl group, X is an ion selected from the groupconsisting of sulfate, sulfonate and halide ions, Z is a member of thegroup, consisting of hydrogen and short chain alkyl groups, Y is amember of the group consisting of hydrogen and carboxylic acyl radicals,

but where Z is alkyl, Y is acyl, n is 0, 1 or 2, and u is 0 or 1.

3. A compound having the formula:

wherein R1, R6 and R7 are aliphatic hydrocarbon groups containing atleast 11 carbon atoms, R, R4 and R5 are alkylene groups containing from2 to 3 carbon atoms, R2 is a hydrophilic group containing an alkyl chainof 1 to 2 carbon atoms, R3 is a short chain alkyl group, X is an ionselected from the group consisting of sulfate, sulfonate and halideions, Z is a member of the group consisting of hydrogen and short chainalkyl radicals, n is 0, 1 or 2, and y is 0 or 1.

4. A compound having the formula:

where R1, R5. and R7 are aliphatic hydrocarbon groups containing atleast 11 carbon atoms, R, R1 and R5 are alkylene groups containing from2 to 3 carbon atoms, R2 and R3 are short chain alkyl groups, X is an ionselected from the group consisting of sulfate, sulfonate and halideions, n'is 0,1 or 2, and y is 0 or 1.

5. A compound having the formula:

wherein R1 and R7 are hydrocarbon groups containing at least 11 carbonatoms, R, R4 and R5 10 are alkylene groups containing 2 to 3 atoms and nis 0 or 1.

6. A compound having the formula:

carbon where R1 and R1 are hydrocarbon groups containing at least 15carbon atoms, R, R1 and Rs are alkylene groups containing from 2 to 3carbon atoms, R2 is a hydrophilic group containing an alkyl chain of 1to 2 carbon atoms, R3 is a short chain alkyl group, X is an ion selectedfrom the group consisting of sulfate, sulfonate and halide ions, Z is amember of the group consisting of hydrogen and short chain alkylradicals, 'Y is a. member of the group consisting of hydrogen andcarboxylic acyl radicals, but Where Z is alkyl, Y is acyl, n is 0,1 or2, and y is 0 or 1.

8. A compound having the formula:

( E IOY EZO wherein R1, R6 and R1 are hydrocarbon groups containing atleast 15 carbon atoms, R, R4 and Rs are alkylene groups containing 2 to3 carbon atoms, R2 is a hydrophilic group containing an alkyl chain of 1to 2 carbon atoms, R3 is a short chain alkyl group, X is an ion selectedfrom the group consisting of sulfate, sulfonate and. halide ions, Z is amember of the group consisting of hydrogen and short chain alkylradicals, n is 0. 1 or2,andyis0or1.

9. A compound having the formula:

( iloy iio t, 1 is wherein R1 and R1 are hydrocarbon groups containingat least 15 carbon atoms, R, R4 and R5 are alkylene groups containingfrom 2 to 3 carbon 11 atoms, Y is a carboxylic acyl 0, 1 or 2. 1 7

11. A compound 'having' the formula:

01139501" CHaPSOa' where-R1 and R7 are hydrocarbon groups containing atleast 15 carbon atoms, R, R4 and R5 are .alkylene groups containing 2 to3 carbon atoms.

and n is 0 or 1.

- 12,. A eompound having the formula:

radical; and 'n is wherein: R1 andR'z are hydrocarbon groupscontaining'at least 15 carbon atoms, R, R4 and R5 'ar'e alkylene' groupscontaining. 2 to 3 carbon atomsand n is Q or 1. V :14. A'compound havingthe formula:

wherein R1 and Rrare hydrocarbon groups containing at least 15 carbonatoms; R, R4 and R5 are alkylene groups containing 2 to 3 carbon atoms.Y is a member of the group consisting of hydrogen and carboxylic 'acylradicals, and n is 0, 1 or 2.

LEWIS O. GUNDERSON.

REFERENCES CITED The following references are of record in the file 'ofthis patent:

V UNITED STATES PATENTS Number Name Date 1,924,698 Neelmeier et a1. Aug.29, 1933 2,008,649 Ulrich July 16, 1935 2,259,650 Maxwell Oct. 12, 19412,357,598 Mauersberger Sept. 5, 1944 2,425,392 Robinson et a1 Aug. 12,1947 2,468,086 Latham et al. Apr. 26, 1949

13. A COMPOUND HAVING THE FORMULA: